Sulfonamide compouunds



United States Patent 0 3,183,266 SULFONAMIDE COMPOUNDS Edwin A. Matzner,St. Louis, Mo., assignor to Monsanto Company, a corporation of DelawareNo Drawing. Filed July 18, 1962, Ser. No. 210,836 6 Claims. (Cl.260-556) The present invention relates to novel chemical compounds andmore particularly to novel sglfo rgl idimpounds and to processes forpreparing t ese compounds. The present invention further relates tonovel compounds which accelerate or pwtejhfl leasuwflom oxygen releasincom unds in a ueous media and which are useful in bleaching and whingoperations. Ifie term oxygen releasing compound as used herein isintended to include hydrogen peroxide and all compounds which, whenplaced in water, form hydrogen peroxide.

sulfonamide compounds are compounds whose molecules contain an S0 groupin which the sulfur atom is linked to a nitrogen atom. A number of thesecompounds, specifically the so-called sulfa drugs, includingsulfadiazine, sulfa-guanidine, sulfamerazine, sulfanilamide,sulfapyridine, sulfathiazole and the like are well known and have beenwidely used as drugs in combating bacterial infections. These and othersulfonamides cause ts'itftgl;

of the prior art have occasionally been employed in the manufacture ofdyes and/ or dye intermediates.

The novel sulfonamide compounds of the present invention have a novel,unrelated and unexpected utility, namely the acceleration and/ orpromotion of the bleaching activity of oxygen releasing compounds notpossessed by the above mentioned sulfonamides.

Detergent compositions containing an oxygen releas ing compound, forexample, an inorganic per-salt, such as an alkali metal perborate orpercarbonate, or a peroxide such as urea peroxide have been disclosedheretofore as useful for washing and bleaching purposes. Although suchcompositions provide a satisfactory bleaching action when they are usedin water at or near the boiling point (e.g., 95 C100 C.), the bleachingactivity is unsatisfactory when the water is at lower temperature, thatis temperatures below 75 C. Detergent and/or bleaching compositionscontaining oxygen-releasing compounds thus have the disadvantage ofbeing unsatisfactory for many uses such as the washing and/or bleachingof textiles and fabrics which cannot withstand higher temperatures, thatis, temperatures above about 70 C. or

when it is desired to use washing media at lower temperatures.

Such disadvantages have been recognized and the prior art indicates thatattempts have been made to find compounds which would promote oraccelerate the release of oxygen-releasing compounds in water at lowtemperature (e.g., 50 C.70 C.) with the goal of providing more effectivebleaching activity and washing activity of such oxygen releasingcompounds.

Examples of such prior art compounds are those disclosed in thefollowing: US. Patent 2,898,181, issued August 4, 1959, discloses theuse of certain carboxylic acid amides, such as acetamide or acrylamideto accelerate or promote the release of oxygen from aqueous solutionscontaining inorganic per-salts; US. Patent 2,955,905, issued October 11,1960, discloses the addition of esters such as the benzoyl esters ofalkali metal phenol sulfonates and glucose penta-acetate asoxygenreleasing promoters to washing compositions containing inorganicper-salts; German Patent 1,081,181, published July 8, 1955, disclosesthe addition of certain compounds such as malonitrile or ethylenedicyanide in compositions containing inorganic pre-salts; and GermanPatent 1,038,693, published November 22, 1956, discloses cer- 3,183,266Patented May 11, 1965 position tends to decompose, resulting in a lossof available oxygen therefrom, when the compositions are stored undernormal storage conditions for periods of from one week to severalmonths.

It has presently been found that the novel sulfonamide compounds of theinstant invention are, surprisingly, highly effective in accelerating orpromoting the bleaching properties and the release of oxygen fromoxygenreleasing compounds in water at temperatures as low as 40 C.Additionally these novel compounds overcome the disadvantages ofinstability, above-referred-to, of the prior art compounds heretoforedescribed for use with oxygen-releasing compounds.

It is one object of this invention to provide novel sulfonamidecompounds.

It is a further object of this invention to provide processes forpreparing these novel sulfonamide compounds.

It is another object of this invention to provide a class of novelsulfonamide compounds which are useful in promoting and/or acceleratingthe release of oxygen from oxygen-releasing compounds in water.

It is a further object of the present invention to provide a class ofnovel N-acyl, alkysulfonamides which will increase the bleaching andwashing efficiency of oxygen releasing agents in water at temperaturesas low as 50 C.

Still further objects and advantages of the present invention aredisclosed in and will become apparent from the following description andthe appended claims.

The present invention provides a class of N-substituted, N-acylalkylsulfonamides having the general formula Acyl radical where R, and Rare organic radicals, at least one of which is an aliphatic radical, andwhere R; is an alkyl group. Compounds of this class are generallystable, crystalline solids when pure, have a limited, but effective,solubility in water and are useful in increasing the bleachingefliciency of oxygen-releasing compounds when incorporated therewith inwater. Such compounds, where R, is an alkyl group containing 10 carbonatoms or less, are usually readily obtainable in crystalline form. Al-

EXAiliNE kyl sulfonamides of this class may also be employed in drycompositions containing oxygen-releasing compounds and such compositionsare generally stable with respect to loss of available oxygen whenstored under ordinary storage conditions for prolonged periods of time,that is, generally for periods of six months or longer.

The term N-acyl as used herein is intended to include the structuredesignated parenthetically in Formula I. Thus when R is an aliphaticgroup or radical the N- acyl structure is an alkanoyl group or radical.When R is an aromatic group or radical the N-acyl structure is an aroylgroup or radical. In the above formula, the alkyl group designated as R,may have as many as 20 or more carbon atoms, however, compounds in whichR contains more than 10 carbon atoms often have limited water solubilityand thus are not as useful for oxygen-releasing compound formulations.Thus, particularly suitable alkylsulfonamides are those in which thealkyl group (R in the above structure), includes, alkyl groups having astraight or branched chain for example, methyl ethyl, npropyl,isopropyl, n-butyl, isobutyl, secbutyl, t-butyl, namyl, iso-amyl,n-hexyl, isohexyl, n-heptyl, isoheptyl, noctyl, iso-octyl, 2-ethylhexyl, etc. groups or radicals.

Particularly advantageous N-substituted N-acyl alkylsulfonamides of thepresent invention and falling within the scope of the above formula areN-substittued, N-acyl alkylsulfonamides having the general formula R] OR3sO21 Rl (II) where R and R are organic radicals at least one of whichis a aliphatic radical and where R; is an alkyl group preferably havingfrom 1 to carbon atoms. Compounds of this class include, for example,N-substituted N-acyl methyl-, ethyl-, or butylsulfonamides and, whenpure, are stable crystalline solids. When the compounds containimpurities, some of them are sometimes oily liquids. However, all suchcompounds generally have sufiicient water solubility to be useful inincreasing the bleaching efficiency of oxygen-releasing compounds inwater at relatively low temperatures, e.g., temperatures as low as 40 C.

One particularly useful group of novel N-substituted, N-acylalkylsulfonamides falling within the scope of Formula I comprisescompounds where one of the organic radicals R or R is an aliphaticradical and the other is an aromatic radical, preferably R is analiphatic and R is an aromatic radical, and where R, is an alkyl group.Another group of particularly useful compounds falling within the scopeof Formula I comprises compounds where R; and R are like or dissimilaraliphatic radicals and R is an alkyl group.

The aliphatic radicals of R and/or R in either or both of the aboveformulae perferably contain from 1 to 10 carbon atoms in the aliphaticgroup. Although such aliphatic radicals may contain more than 10 carbonatoms, for example, up to 30 carbon atoms, compounds containing morethan 10 carbon atoms, often have limited water solubility. Thus, theunsubstituted aliphatic hydrocarbon groups or radicals in the abovestructure may, and, preferably do, include, for example, alkyl groups orradicals having a straight or branched chain, e.g., methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, tbutyl, n-amyl,iso-amyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, iso-octyl,2-ethyl hexyl, etc. groups or radicals.

The substitutents of the substituted aliphatic groups or radicals maybe, for example, halogen atoms, hydroxyl, sulfo, nitro, carboxy-,alkoxy-, carbalkoxy-, amino, alkyl or carboxyl groups or radicals toprovide the aforementioned substituted groups or radicals.

The unsubstituted aromatic groups or radicals may be, for example,phenyl, pyridyl, benzyl, alpha and beta naphthyl, quinolyl, anthryl,benzquinolyl and the like. The substituents of substituted aromaticgroups or radicals may include halo-, hydroxyl, nitro-, sulfoand alkylsubstituted groups or radicals. The alkyl substituted aromatic groups orradicals preferably contain from 1 to carbon atoms in the alkyl group.

Illustrative examples of some specific N-substituted, N- acylalkylsulfonamides of this invention falling within the scope of FormulaI and which are contemplated by this invention are:

N-ethyl,N-acetyl,methyl-, ethyl, or propylsulfonamideN-ethyl,N-benzoyl,methyl-, ethyl-, or butylsulfonamideN-phenyl,N-propionyl,methyl-, ethyl-, or propylsulfonamideN-n-propyl,N-acetyl,methyl-, ethyl-, or butylsulfonamideN-isopropyl,N-chloracetyl,methyl-, ethyl-, or propylsulfonamideN-hydroxymethyl,N-benzoyl,amyl-, hexyl-, or heptylsulfonamideN-ethyl,N-beta-phenylacetyl,methyl-, ethyl, or propylsulfonamideN-methyl,N-hydrocinnamoyl,methyl-, or ethylsulfonamideN-(4-hydroxycyclohexyl),N-chloroacetyl,methyl-, or ethylsulfonamideN-(beta-carboxymethyl),N-(benzoyl)-methyl-, ethyl-, or

butylsulfonamide N-(4-pyridyl),N'propionyl,methyl-, ethyl-, orpropylsulfonamide N-formyl,N-(p-bromobenzoyl),methyl-, orethylsulfonamide N-carbethoxymethyl,N-(alpha-napthoyl)methyl-, orethylsulfonamide N-methyl,N- (p-nitrobenzoyl ,methyl-,

amide N-acetyl,N-p-hydroxymethyl,methyl-, ethyl-, or butylsulfonamideN-phenyl,N-butyroyl,methyl-,

amide N-nitroethyl,N-acetyl,methyl,ethyl-, or butylsulfonamide Apreferred group of N-substituted, N-acyl, alkylsulfonamides fallingwithin the scope of Formula II are compounds where R or R or both, areunsubstituted aliphatic radicals, and R is an alkyl group. Anotherpreferred group of compounds are those where R or R is an unsubstitutedaliphatic radical and the other is an unsubstituted aromatic radical,preferably R is an unsubstituted aromatic radical and R is anunsubstituted aliphatic radical, and R is an alkyl group.

Particularly preferred compounds of this invention which have been foundto be especially useful in promoting or accelerating the release ofoxygen from oxygenreleasing compounds are N-substituted, N-acylalkylsulfonamides having the following general formulae orethylsulfonethyl-, or propylsulfon- N-methyl,N-acetyl,methylsulfonamideN-phenyl,N-acetyl,methylsulfonamide N-methyl,N-benzoyl,methylsulfonamideN-methyl,N-benzoyl,ethylsulfonamide N-methyl,N-benzoyl,butylsulfonamideThe N-substituted, N-acyl, alkylsulfonamides of this invention may beprepared by a process which comprises mixing and reacting anN-substituted alkylsulfonamide such as an N-aliphatic or an N-aromaticsubstituted sulfonamide with an acyl compound such as, for example, analkanoyl or an aroyl compound. In such reaction the N-substitutedalkylsulfonamide and the acyl compound should be so selected and reactedthat a compound charfonamides having the following general formulaewhere R or R or both, are aliphatic radicals, and R is an alkyl group,is formed. Although the amounts of N-substituted alkylsulfonamides andacyl compounds may vary widely, they are preferably reacted in a molratio of from about 1.5:1 to 121.5, more preferably a mol ratio of about1:1.

A suitable process for preparing an N-aliphatic, N- alkanoyl,alkylsulfonamide of this invention comprises mixing and reacting anN-aliphatic alkylsulfonamide with an alkanoyl compound such as, forexample, an alkanoyl halide until an N-substituted, N-acylalkylsulfonamide having the above general formula is formed. In theproduct formed by this process, R and R in the above described formulaare aliphatic radicals and R is an alkyl group.

A suitable process for preparing an N-aliphatic, N- aroyl sulfonamide ofthis invention comprises mixing and reacting an N-aliphaticalkylsulfonamide with an aroyl compound, for example, an aroyl halide,until an N-substituted, N-acyl sulfonamide having the above describedgeneral formula is formed. In the product formed by such a process, R ofthe above formula is an aromatic group or radical and R is an aliphaticgroup or radical and R is an alkyl group.

A suitable process for preparing an N-aromatic, N- alkanoyl sulfonamideof this invention comprises mixing and reacting an N-aromaticalkylsulfonamide with an alkanoyl compound, until an N-substituted,N-acyl alkylsulfonamide having the above general formula is formed. Inthe product formed in this process R in the above formula is analiphatic group or radical and R is an aromatic group or radical.

The N-substituted alkylsulfonamides which may be employed in suchprocess are characterized in having the formula:

R: R3SOgI I-H where R is an alkyl group as hereinbefore described and Ris an organic radical, e.g., either an aliphatic or an aromatic radicalas hereinbefore described.

The N-substituted alkylsulfonamides may be readily obtained by reactinga suitable alkylsulfonyl chloride or a mixture of alkylsulfonylchlorides with an organic amine in a liquid alkaline medium, thereaction being exemplified by the following equation I'M Ra-SO CI R NH;R SO -NH 1101 where R and R have the same meaning and significance ashereinbefore described.

The organic amines which may be employed in the above process include,for example, alkylamines such as methylamine, ethylamine, butylamine,cylcohexylamine and the like and arylamines such as, for example,aniline, naphthylamine, aminopyridine, amino-anthracene, etc.

The acyl compounds which may be reacted with the above-describedN-substituted alkylsulfonamides in accordance with the processes of thisinvention include organic acid anhydrides having the formula (R CO) O.

organic esters having the formula R COOX, and acyl halides having theformula R COY. In the above formula R is an organic radical ashereinbefore described, and X is an alkyl or an aryl group or radicaland Y is a halogen preferably chlorine or bromine.

Examples of acyl compounds which may be employed in the processes ofthis invention include alkanoyl compounds, for example, alkyl acidanhydrides such as acetic anhydride, butyric anhydride and the like;alkanoyl halides such as acetyl chloride, acetyl bromide, thecorresponding butyroyl halides and the like; aroyl compounds such as,for example, benzoic anhydrides, benzoyl chloride or bromide and thelike; mixed anhydrides, for example, acetyl benzoate, butyroyl benzoate,etc., and aroyl esters such as benzoyl acetate, benzoyl butyrate, etc.;carboxylic acid esters, such as ethyl benzoate, benzyl propionate, ethylacetate, ethyl propionate and the like.

The particular N-substituted alkylsulfonamide or mixture ofN-substituted alkylsulfonamides and the particular acyl compoundemployed in the processes of this invention will depend upon theparticular N-substituted, N- acyl, alkylsulfonamide desired. When theNsubstituted alkylsulfonamide is an N-aromatic alkylsulfonamide the acylcompound is an alkanoyl compound. However,

when the N-substituted alkylsulfonamide is an N-aliphaticalkylsulfonamide the acyl compound may be either an alkanoyl or an aroylcompound.

The N-substituted, alkylsulfonamide may be mixed and reacted with any ofthe above-described acyl compounds either in situ, that is, in theabove-described liquid alkaline medium or alternatively such sulfonamidemay be recovered as a solid and thereafter reacted with the acylcompound. When it is desired to carry out the reaction in situ the acylcompound, for example, either an alkanoyl compound or an aroyl compound,is slowly added, with agitation to a mixture comprising a liquidalkaline medium and the N-substituted alkylsulfonamide. During and/ orafter the addition of the acyl compound the mixture may be heated ormaintained at a temperature in the range of between 30 C. and 200 C.until the N-substituted, N- acyl, alkylsulfonamide is formed. Althoughtemperatures below 30 C. may be employed the reaction tends to proceedmore slowly than may be desirable. Higher temperatures which may beemployed are, in general, limited by the boiling point of the liquidalkaline medium.

The time required for the N-substituted, alkylsulfonamide to completelyreact with the acyl compound will vary considerably depending upon theamount of the reagents to be reacted, the alkaline medium used and thetemperature employed. Complete reaction normally occurs over a period offrom about 30 minutes to 4 hours, the smaller quantities of reagents andhigher temperatures of the reaction medium requiring shorter reactiontimes.

After the reaction is completed the N-substituted, N- acyl,alkylsulfonamide may be recovered by neutralizing the liquid alkalinemedium with a suitable acid and thereafter concentrating and cooling theneutralized medium to precipitate out the crystalline compound.Alternatively, the N-substituted, N-acyl, alkylsulfonamides may berecovered from the neutralized medium by extraction in awater-immiscible, low boiling point solvent such as, for example,ligroin, carbon tetrachloride or chloroform which can be readily cooledand/ or evaporated and from which crystalline compounds may be directlyrecovered.

When the N-substituted alkylsulfonamides are available or have beenpreviously prepared such compounds may be dissolved in a liquid alkalinemedium and mixed and reacted with an acyl compound as above-described oralternatively, since the acyl compounds are usually liquid organicsolvents having boiling points ranging from about 30 C. to 200 C., theN-substituted alkylsulfonamide may be added directly to an excess of theacyl compound and heated, preferably at or near the boiling point of theacyl compound, more preferably by refluxing for from 30 minutes to 4hours, until the reaction is completed. The excess acyl compound maythen be removed by distillation to obtain the crystalline N-substituted,N- acyl, alkylsulfonamide.

Where the boiling point of the acyl compound is below 30 C., the acylcompound may be mixed with a higher boiling liquid, such as for example,glacial acetic acid and the N-substituted alkylsulfonamide added theretoand heated, preferably by refluxing, until the desired compound isformed. The compound may then be separated or crystallized asabove-described.

The N-substituted alkylsulfonamides may be prepared by a process whichcomprises mixing and reacting about one molecular proportion of ahereinafter described organic amine, e.g., an alkyl or an aryl amine,with about one molecular proportion of an alkylsulfonyl chloride in aliquid alkaline medium until an N-alkyl or an N-aroyl alkylsulfonamideis formed and thereafter mixing and reacting the N-substitutedalkylsulfonamide so formed with a hereinbefore described acyl compound,e.g., an alkanoyl or an aroyl compound, at a temperature in the range offrom about 50 C. to about 200 C., until an N-substituted, N-acyl,alkylsulfonamide is formed. The particular organic amine and acylcompound are so selected so that a compound falling within the generalscope of Formula I, hereinbefore described, is formed.

A wide variety of liquid alkaline media may be employed in such processincluding non-aqueous, watersoluble, alkaline organic liquids such aspyridine or lutidene or aqueous alkaline liquids such as aqueoussolutions of alkali metal hydroxides or alkali metal carbonates. It ispreferred that the liquid alkaline medium be one in which the organicamine is soluble for the reaction usually proceeds slowly if the organicamine is insoluble or partially soluble in the medium. In order toinsure a relatively rapid reaction between the organic amine and thealkylsulfonyl chloride, it is preferred that the organic amine besoluble in the liquid alkaline medium in an amount of at leastpreferably at least 10%, by weight in the medium. Since the reactionbetween the organic amine and the alkylsulfonyl chloride is exothermic,it is preferred that the organic amine be first dissolved in the liquidalkaline medium and that the alkylsulfonyl chloride be slowly added withagitation, preferably by mechanical means, to the solution. Ifdesirable, the liquid medium may be cooled during the addition of thealkylsulfonyl chloride and maximum yields of N-substituted,alkylsulfonamide are usually obtained when the process is carried out attemperatures below 45 C., preferably at temperatures in the range ofabout C.- C. Although temperatures below 30 C. may be employed there isno significant advantage and the reaction time is usually significantlyprolonged.

Thus, by way of illustration, N-methyl, N-acetyl alkylsulfonamides ormixtures thereof may be prepared by mixing and reacting an appropriatealkylsulfonyl chloride, for example, methyl-, or l-butylsulfonylchloride or mixtures thereof and methylamine in a liquid alkaline mediumin a molecular ratio of about 1:1 to obtain an N-methyl alkylsulfonamidewhich in turn may be reacted with alkanoyl compounds such as aceticanhydride or acetyl chlo-' ride to obtain an N-methyl, N-acetylalkylsulfonamide. Also by Way of further illustration, N-methyl,N-benzoyl, alkylsulfonamides may be prepared by mixing and reacting anappropriate alkylsulfonyl chloride and methylamine in a liquid alkalinemedium in a molecular ratio of about 1:1 to obtain an N-methylalkylsulfonamide which may then be mixed and reacted with aroylcompounds such as benzoic anhydride, benzoyl chloride or benzoyl acetateto form an N-methyl,N-benzoyl,alkylsulfonamide.

Any of the N-substituted, N-acyl, alkylsulfonamides of this invention ormixtures thereof may be mixed with a wide variety of organic and/orinorganic oxygen-releasing compounds to provide novel bleachingcompositions. However, the alkylsulfonamides of Formulae II or III,hereinbefore described have been found generally preferable. Examples oforganic oxygen-releasing compounds include organic peroxides such asurea peroxide, benzoyl peroxide, methyl ethyl ketone peroxide and thelike. Examples of inorganic oxygen-releasing compounds include inorganicperoxides such as alkaline-earth metal peroxides, for example, calcium,magnesium, zinc and barium peroxides. Other suitable inorganic peroxidesinclude alkali metal carbonate peroxides such as sodium carbonateperoxide, and alkali metal pyrophosphate peroxides such as sodiumpyrophosphate peroxide. Particularly suitable inorganic oxygen-releasingcompounds include inorganic persalts such as ammonium and metalpersulfates, perchlorates and perborates. Of these per-salts, watersoluble alkali metal persulfates and perborates are preferred and alkalimetal perborates, especially sodium and potassium perborates areparticularly preferred.

Useful bleaching compositions comprise, as noted above, a mixture of anoxygen-releasing compound and one or more of the novel compounds of thisinvention. These ingredients can be used in the compositions in variousproportions depending upon whether the compositions are to be used as ableaching composition or a washing composition or both. However, in mostinstances, the

8 compositions contain either an organic or an inorganc oxygen-releasingcompound and from about 0.1 to about 2.0 mols, per mol ofoxygen-releasing compound of any of the N-substituted N-acylsulfonamides.

The novel compounds of this invention promote and accelerate the releaseof a greater amount of oxygen from oxygen-releasing compounds in waterat 50 C.'80 C. than occurs when such oxygen-releasing compounds aredissolved in water at these temperatures in the absence of such novelcompounds.

Suitable compositions comprise a mixture of an inorganic per-salt suchas an alkali metal perborate and from about 0.1 to about 2.0 mols, permol of perborate of any one or more of the novel compounds of thisinvention and one or more of an inorganic detergent builder salt and/oran inorganic diluent salt, and/or an organic surfactant.

A further understanding of the novel compounds of this invention as wellas the utility and the processes of preparing such compounds may beobtained from the following specific examples which are intended toillustrate the invention, but not to limit the scope thereof, parts andpercentages being by weight unless otherwise in- Example I To a 2 literreaction vessel containing 1.5 liters of a 5 weight percent solution ofsodium hydroxide, there was added, with agitation grams of an aqueoussolution containing 30 percent by weight (1 gram mol) of monomethylamine. Thereafter, at room temperature (25 C.) and while agitation wascontinued, there was slowly added grams (1 gram mol) of methylsulfonylchloride. The resulting reaction mixture was stirred for 4 hours at roomtemperature (25 C.) and filtered. The filtrate was slightly acidified bythe slow addition of 180 grams of concentrated hydrochloric acid.

N-methyl-methylsulfonamide did not separate at this point in view of itswater solubility. The solution was thus evaporated almost to dryness andthe mushy residue extracted with four 100 ml. portions of methylalcohol. The extracts were combined, the methyl alcohol distilled offand the residue, consisting of N-methyl-methylsulfonamide, transferredto a 2 liter reaction vessel equipped with a heater and refluxcondenser. To this reaction vessel containing N-methyl,methylsulfonamide, there was slowly added 800 grams of acetic anhydride.The reaction mixture was heated at a temperature of about C. for 3.5hours and thereafter cooled in an ice bath. After the reaction mixturehad cooled, ice water (3 C.) was slowly added to the reaction mixture toconvert the excess acetic anhydride to acetic acid. During the additionof the ice water a white crystalline material precipitated from theaqueous acetic acid solution. The crystals were separated from the cold(5 C.) aqueous acetic acid solution and recrystallized in 70% aqueousethanol. A yield of 115 grams of white crystalline N-methyl, N-acetyl,methylsulfonamide was obtained. The melting point of the crystals wasdetermined and found to be about 40 C.

Elemental analysis of a portion of the crystalline material showed it tocontain the following elements in the amounts given below and comparedwith the theoretical elemental content of N-methyl, N-acetylmethylsulfonamide.

The elemental analysis was in substantial agreement witth the formulafor N-methyl, N-acetyl, methylsulfonamide. The yield of 115 grams was75% of that theoretically possible based on the methylsulfonyl chloridecharged.

The infrared absorption of the compound of this example was determinedusing potassium bromide pellets. The infrared absorption peaksestablished the presence of 80;, the CN bond and the acyl structure ofthe compound.

Example 11 To a 4 liter, three necked glass reaction vessel equippedwith a mechanical stirrer, thermometer, reflux condenser and heaterthere was charged 1,000 ml. of pyridine and 90 grams (2.9 mols) ofanhydrous liquified methylamine which immediately dissolved in thepyridine. To this solution there was slowly added with cooling andagitation 322 grams (2.8 mols) of methylsulfonyl chloride. The additiontook place over a minute period in order to prevent the reaction, whichwas exothermic, from causing the temperature of the contents of thereaction vessel to rise above 30 C. After the addition was completed,the reaction mixture which consisted of a solution of N-methyl,methylsulfonamide in pyridine was heated to 45 C. and stirred for 30minutes. Thereafter there was slowly added with continuous agitationover a 15 minute period, 394 grams (2.8 mols) of benzoyl chloride. Theresulting reaction mixture was stirred for 3 hours during which time itwas continuously maintained at a temperature of 100 C. The reactionmixture was a solution comprising N-methyl, N-benzoyl, methylsulfonamidein pyridine.

The solution was cooled and the methylsulfonamide compound was extractedfrom the pyridine into chloroform by adding the pyridine to a separatoryfunnel containing 8 liters of chloroform thereby forming a chloroformsolution of the methylsulfonamide. Reaction impurities, includingresidual pyridine were extracted and/ or washed from the chloroformsolution with 2 liters of an aqueous solution containing 10%hydrochloric acid. This procedure was repeated twice after which thechloroform solution was Washed two more times with 1.5 liters of asaturated solution of sodium bicarbonate and finally washed threeadditional times with water. The water was removed from the chloroformsolution by drying it over magnesium sulfate. After refluxing with 25grams of decolorizing charcoal for 2 hours, the solution was filteredand concentrated by evaporating 7.5 liters of the chloroform. Theresidue was recrystallized from boiling ethyl alcohol, and fine whitecrystals were obtained. The crystalline yield was 410 grams or 69% ofthat theoretically possible, based on the methylsulfonyl chlorideinitially charged. The melting point of the crystals was 101 C.

An elemental analysis was conducted on the crystalline material. Theactual elemental content compared with the theoretical elemental contentof N-methyl, N-benzoyl methylsulfonamide is given below:

Element Actual (found) Theoretical (percent) (percent) Carbon 50. 63 50.70 Hydrogen 5. 09 5. Nitrogen 6. 54 6. 57

The elemental analysis was in substantial agreement with the formula forN-methyl, N-benzoyl, methylsulfonamide.

X-ray analysis of the crystals was conducted using nickel filteredcopper K-alpha radiation at a wave length 10 of 1.541 angstroms, X-raydiffraction pattern (with intensities of 1% and greater) was as follows:

Interplanar spacings Relative intensity,

((1) Augstroms percent Infrared absorption analysis of the compound ofthis example was determined using KBr pellets. The infrared absorptionpeaks at the wave lengths indicated in the table below established thepresence of S0 the CN bond and the acyl structure of the compound.

Absorption peaks Relative (wave length in intensity microns) Example IIIThe procedure of Example II was repeated, except that ethylsulfonylchloride was employed in place of methylsulfonyl chloride of Example II.The crystalline compound obtained was N-methyl, N-benzoylethylsulfonamide as indicated by the elemental analysis of the compoundobtained. The compound had a melting point of 108 C.

The actual elemental content, analytically determined and compared withthe theoretical elemental content of N-methyl-N-benzoyl,ethylsulfonamide is given below:

Element Actual (found) Theoretical (percent) (percent) 1 1 X-raydiffraction analysis of the crystals, conducted using the procedures ofthe preceding examples (and with intensities of 3% and greater) was asfollows:

Interplanar spacings Relative intensities,

(d) Angstroms percent Infrared absorption analysis of the compound ofthis example was determined in KBr pellets. The infrared absorptionpeaks and wave lengths indicated in the table below established thegeneral structure, e.g., the CN bond, the SO; group and the acylstructure, of the compound.

Absorption peak Relative (wave length in intensity microns) 3.3 Weak.

6.0 Strong.

6.3 Weak.

7.0 Medium 7.? Strong.

8.5. Medium 9.6 Strong.

10. Weak.

W HHHHHHHHW s s s r'rppp Example IV The procedure of Example II wasrepeated, except that l-butylsulfonyl chloride was employed instead ofthe methylsulfonyl chloride used in Example 11. A yield of 71% of thepossible theoretical yield of the crystalline compound N-methyl,N-benzoyl, l-butylsulfonamide was obtained. The compound had a meltingpoint of 123 C.

An elemental analysis was conducted on the crystalline materialobtained. The actual elemental content of the crystals compared with thetheoretical elemental content of N-methyl, N-benzoyl l-butylsulfonamideis given below.

Element Actual (tound) Theoretical (percent) (percent) An infraredabsorption analysis of the compound was conducted as described in theprevious example. The infrared absorption pattern obtained establishesthe presence of pertinent structural elements, e.g., S0 the CN bond andthe acyl structure of the compound.

Example V To a glass reaction vessel equipped with a mechanical stirrer,there was charged 8 liters of a 5% solution of aqueous sodium hydroxideafter which 220 grams (2.4 mol) of aniline was added to the reactionvessel and dis solved in the NaOH solution. Thereafter there was slowlyadded over a 10 minute period at room temperature (25 C.) and withagitation 258 grams (2.25 mols) of methylsulfonyl chloride. Theresulting mixture was mechanically agitated for 2 hours at roomtemperature (25 C.) after which time it was filtered and acidified with1,000 grams of concentrated hydrochloric acid. A white precipitateconsisting of N-phenyl, methylsulfonamide formed in the reactionmixture. The precipitate was filtered, dried and transferred to a secondreaction vessel equipped with a heater and reflux condenser. One literof acetyl chloride and 800 ml. of glacial acetic acid were added to thereaction vessel thereby dissolving the solid crystals. The resultingsolution was refluxed at a temperature of 52 C- for 2.5 hours. At theend of this time the excess acetyl chloride was distilled off and 3liters of cold (5 C.) distilled water was added to the liquid residue. Awhite crystalline precipitate which formed during the addition of thecold water was separated by filtration washed with a cold (5 C.)saturated solution of sodium bicarbonate and recrystallized from methylalcohol. The crystalline material obtained which consisted of N-phenyl,N-acetyl methylsulfonamide weighed 375 grams amounting to a yield of 78%of that theoretically possible based on the methylsulfonyl chloridecharged. The crystalline material had a melting point of 121 C.

The actual elemental content, analytically determined and compared withthe theoretical elemental content of N-phenyl, N-acetylmethylsulfonamide is as follows:

Element Actual (found) Theoretical (p c (percent) Carbon 50. 62 50. 70Hydroge 5.11 5.20 Nitrogen 6. 40 6. 57

The elemental analysis was in substantial agreement with the formula forN-phenyl, N-acetyl, methylsulfonamide.

X-ray diflraction analysis resulted in the following X- ray diffractionpattern:

Interglanar spacings Relative intensity,

( Angstrom percent 13 The infrared absorption peaks obtained frominfrared absorption analysis of the compound of this example establishthe presence of pertinent structural elements, e.g., S0,, the CN bondand the acyl structure of the compound.

Example VI Two hundred grams of a mixture of alkylsulfonyl chloridescomprising l-butyl sulfonyl chloride, l-pentylsulfonyl chloride,l-hexylsulfonyl chloride, l-heptylsulfonyl chloride and l-octylsulfonylchloride, wherein the average molecular weight of the alkyl groups was80, was reacted with 34 grams of methyl amine and 160 grams of benzoylchloride in accordance with the procedure described in Example II. Twohundred-fifty grams (ap proximately 80% of the theoretical yield, basedon the alkyl sulfonyl chloride mixture charged), of a yellowish waxysolid was obtained. This mixture consisted of a mixture of N-methyl,N-benzoyl alkylsulfonamides in which the alkyl groups corresponded tothose of the starting alkylsulfonyl chlorides. This material was foundto be effective in promoting and/ or accelerating the bleaching activityof aqueous solutions of sodium perborate compositions at temperatures aslow as 50 C.

The infrared absorption pattern of the mixture of this exampleestablished the presence of pertinent structural elements, e.g., the Sgroup, the C--N bond and the acyl structure of the compound.

Example VII Dry mixed compositions containing the following ingredientsin the percentages given in the following table were prepared.

Composition Number Ingredient Sodium dodecylbenzene sulionate Sodiumtripolyphosphate. Tetrasodium pyrophosphate. Sodium silicate Sodiumsulfate 4 Lauryl isopropanol amide 0. N-methyl, N-acetyl, methylsulionmlde N-phenyl, N-aeetyl methylsulfonamide N-methyl, N-benzoylmethylsulfonam e N-methyl, N-benzoyl ethylsulionamide Sodium perborateThe bleaching capacity of each of compositions 1 through 5 wasdetermined by dissolving 0.25% by weight of each composition in water inseparate cylindrical receptacles. The receptacles were provided withmechanical agitation and the solutions therein were maintained at atemperature of C. Each solution had an available oxygen concentration ofabout 11.5 parts per million. The solutions contained a mol ratio ofsodium perborate to acyl sulfonamide of about 1:1.

Eight 5" x 5" swatches of unbleached naturally yellowed muslin wereanalyzed for reflectance (Rd) and (a)+(b) color values on a GardnerAutomatic Color Difference Meter. Two swatches were placed in each ofthe 5 receptacles containing the dissolved compositions and washed for10 minutes. After this period the swatches were dried, pressed and againanalyzed on the Gardner Automatic Colorimeter. The reflectance ARd(brightening) and bleaching efficiency A(a) and A(b) were calculated bysubstracting the difference in readings before and after the washingoperation. The loss of available oxygen was also determined for eachsolution. The results are summarized in the accompanying table.

The Gardner Automatic Color Difference Meter is a tristimuluscolorimeter, that is, it contains three photo 14 cells which measure (1)reflectance (Rd); (2) green to red color (a); (3) blue to yellow color(b).

Composition Available number oxygen 1 loss MM 1 A (a) A(b) I (percent) 1Determined by Iodometric titration of spent wash solutions.

2 Positive values indicate degree of increase of reflectance orbrightening.

Negative values indicate the degree of color disappearance or bleaching.

The above values for loss of available oxygen indicate the release ofoxygen from sodium perborate. By way of contrast a solution of acomposition identical, except that it did not contain the sulfonamide,showed a loss of only 40% of available oxygen. The above results alsodemonstrate that the above compositions bleached and brightened theyellow unbleached muslin. However, solutions of compositions from whichthe acyl sulfonamides were omitted did not bleach or brighten the muslinto any appreciable extent.

Example VIII The bleaching acceleration properties of some of the novelcompounds of this invention are further indicated by the following:

To one liter of standard full strength borate-carbonate pH 10 buffersolution there was added the following.

(1) 0.460 gram of Orange II[P(2-hydroxy-l-naphthylazo)-benzene sulfonicacid-sodium salt] (2) 2 grams of a detergent having the compositionIngredient: I Percent Sodium dodecylbenzenesulfonate 25.0Laurylisopropanol amide 3.0 Sodium silicate 6.0 Sodium tripolyphosphate28.0 Tetrasodium pyrophosphate 12.0 Anhydrous sodium sulfate 17.3 Sodiumcarboxymethyl cellulose 0.7 Moisture 8.0

recording the time, the materials indicated in the following 7 tablewere added to the numbered tubes containing the orange dye-detergentsolution.

Dye concentration (percent of orginal), Tube Compound minutes 1 Solutiononly 100 100 100 100 2 0.080g.sodiumperborate 100 81 63 53 3 0.080 g.sodium perborate N- 100 76 54 23 mectihyl, N-acetyl, methylsultonaml e.4 0.080 g. sodium perborate N- 100 78 52 20 phednyl, N -aeetyl,methylsultonam1 e. 5 0.080 g. sodium perborate N- 100 69 41 1! methyl,N-benzoyl, methylsulfonamide. 0.080 g. sodium perborate N- 100 73 14methyl, N-benzoyl, ethylsultonamide. 7 0.080 g. sodium perborate N- 10075 48 18 methyl, N-benzoyl, 1,-butylsulionarnlde.

15 In the above table the N-substitutcd N-acyl alkylsulfonamides wereadded in equimolar amounts with respect to the sodium perborate, thatis, 0.00052 gram mol of each compound was added to the tube asindicated.

The results demonstrate that the compounds of this in- 5 ventioneffectively promote the bleaching of standard dyes when in solution at60 C.

The novel compounds disclosed in this application have been disclosed asincorporated components of novel bleaching and washing compositions inmy copending U.S. patent, application Serial No. 181.449, filed in theU.S. Patent Office, March 21, 1962.

What is claimed is:

1. A compound of the formula 2. A compound of the formula alkyl Alkyl-SO N-C O-phenyl wherein alkyl is from 1 to 10 carbon atoms.

3. A compound of the formula Alkyl-S 01-N-C O-phenyl wherein alkyl isfrom 1 to 10 carbon atoms.

4. N-methyl, N-benzoyl, methylsulfonamide. 5. N-methyl, N-benzoyl,ethylsulfonamide. 6. N-methyl, N-benzoyl, l-butylsulfonamide.

References Cited in the file of this patent UNITED STATES PATENTS1,9l6,604 Carswell et a1 July 4, 1933 2,383,859 Hentrich Aug. 28, 1945FOREIGN PATENTS 621,550 Great Britain June 6, 1961 692,651 Great BritainJune 10, 1953 873,925 France Apr. 13, 1942 OTHER REFERENCES Kostsova:Journal of General Chem., U.S.S.R., vol. 23,

Chemical Abstracts, volume 50, p. 4840 (1956).

Vandi et al.: J. Org. Chem., vol. 26, pp. 1136-8 (1961 Kostsova et al.:Zhur. Obsch. Khim., vol. 25, pp. 2497- 2503 (1955).

1. A COMPOUND OF THE FORMULA
 4. N-METHYL, N-BENZOYL, METHYLSULFONAMIDE.